2.6- Diamino-3,5-dinitrotoluene

Highly pure salts of 2,3,5,6-tetraaminotoluene can be produced by the reduction of 2,6-diamino-3,5-dinitrotoluene [10]. 2,6-Diamino-3,5-dinitrotoluene can be made by the nitration of 2,6-dichlorotoluene followed by a reaction with ammonia. The 2,3,5,6-tetraaminotoluene salt is precipitated as a clean product with a purity of more than >99%. 

Dichlorobenzene, aminotoluene, nitrotoluene isomers, diamino-toluene, and dinitrotoluene isomers... 

Haidour and Ramos (1996) analyzed the degradation products of 2,4,6-trinitrotoluene, 2,4-dinitrotoluene, and 2,6-dinitrotoluene by the bacterium Pseudomonas sp. clone A under aerobic conditions. Reduced 2,4,6-trinitrotoluene metabolites, which were not used as a nitrogen source by this bacterium, were 2-hydroxyamino-4,6-dinitrotoluene, 4-hydroxyamino-2,6-dinitrotoluene, and 2,4-diamino-6-nitrotoluene. 

C. bifermentam strain CYS-1 was also isolated from our anaerobic bioreactor. Shin Crawford (1995) examined the ability of CYS-1 to degrade TNT cometabolically in various defined media. This strain could overcome the toxicity of and degrade >150 ppm TNT in liquid media supplemented with a rich cosubstrate such as yeast extract or trypticase soy, given an appropriate inoculum ( 107 CFU/ml). Furthermore, it was found that CYS-1 could degrade TNT which contaminated a sandy loam soil. The degradation of TNT proceeded through the transient intermediates 4-amino-2,6-dinitrotoluene and 2,4-diamino-6-nitrotoluene. 

In addition to the compds in Table 1, they obtained evidence for 2-hydroxylamino4,6-dinitro-toluene, 2,4-diamino-6-nitrotoluene, 2,6-diamino-4-nitrotoluene, 2,4,6-trinitrobenzoic acid and (with considerable lack of confidence) 2,4,6-tri-nitrobenzyl alcohol. They confirmed that 2,2 6,6,-tetranitro4,4f azoxytoluene is not a constituent of fresh urine, but may form from 4-hydroxylamino-2,6-dinitrotoluene when the urine is allowed to stand or during isolation procedures. They saw almost no unmetabolized TNT in urine. The urine of orally dosed rats and mice had a bright red color, but not that of dogs and rabbits. The radioactivity of labeled TNT was mainly excreted, but some ended up distributed in various organs... 

TNT is readily absorbed through skin, especially when skin is moist. It is excreted in urine more than in feces some is found in bile. The major biotransformation reaction is nitroreduction and, to a lesser extent, oxidation. The main metabolite formed by nitroreduction seems to be 4-amino-2,6-dinitrotoluene (4-ADNT). Other metabolites include 2-amino-4,6-dinitrotoluene (2-ADNT), 2,4-diamino-6-nitrotoluene, and 2,6-diamino-4-nitrotoluene. The metabolites are excreted in the urine as glucuronide conjugates and in the free form. Ring oxidation products of TNT such as trinitrobenzylalcohol, trinitrobenzoic acid, and simultaneous oxidation and reduction metabolites such as 2,6-dinitro-4-amino-benzylalcohol and 2,6-dinitro-4-amino-m-cresol are of less importance. Untransformed TNT is also excreted in the urine. ADNT and TNT concentrations were found in workers in explosives factories. 4-ADNT excretion was reported to be complete within 3M days after exposure. However, another study reported detectable urine concentration of ADNT in explosives workers even after 17 days away from the workplace. 

Various modern products may serve as sources for trace amounts of PAA. The origins, known hazards, release restrictions and environmental fate of PAA derived from azo dyes have been reviewed2. The metabolism of nitroarenes is closely linked to that of aromatic amines, as shown in a simplified way in equation 369. Gloeophyllum trabeum cultures spiked with TNT show formation of nitroaromatic amines such as 2-ami no-4,6-dinitrotoluene, 4-amino-2,6-dinitrotoluene and 2,4-diamino-6-nitrotoluene. Also, autoxi-dation of the methyl group of TNT or its metabolites may take part in the degradation process, as shown by the presence of Schiff bases and oligomeric and polymeric species detection and determination of the analytes after LLE and concentration were by HPLC-UVD or GC-MS70. 

TNT Amino-dinitrotoluenes Diamino-nitrotoluenes Hydroxylamino-dinitrotoluenes Tetranitro-azoxynitrotoluenes (High organic) Aerobic... 

Figure 2. Proposed pathway for transformation of 2,4,6-TNT [5]. I, 2,4,6-TNT II, 4-hydroxylamino-2,6-dinitrotoluene III, 4-amino-2,6-dinitrotoluene IV, 2,4-diamino-6-nitrotoluene V, 2-hydroxylamino-4,6-dinitrotoluene VI, 2-amino-4,6-dinitrotoluene VII, 4,4 -azoxycompound VIII, 2,2 -azoxycompound IX, 2,4,6-triaminotoluene.

Trinitrotoluene (TNT) and its biotransformation products (2,6-diamino-4-nitrotoluene, 2,4-diamino-6-nitrotoluene, 4-amino-2,6-dinitrotoluene, and 2-amino-4,6-dinitrotoluene) were baseline resolved on tandem Cig/cyanopropyl columns (A = 230nm) using a 60.5/25/14.5 water/methanol/THF mobile phase. Elution was complete in <20 min [182]. 

The anaerobic metabolites of 2,4-dinitrotoluene and 2,6-dinitrotoluene (2,6-diami-notoluene, 2-hydroxylamino-6-nitrotoluene, 2-nitroso-6-nitrotoluene, 2-amino-6-nitrotoluene, 3,3 -diamino-2,2 -dimelhylazoxybenzene, 2,2 -dimethyl-3,3 -dinitro-azoxybenzene) were baseline resolved on a C g column (2 = 250nm) using a complex 65-min 15/85 - 60/40 acetonitrile/water gradient [944], Detection limits of 5 ng injected were reported. A linear concentration range of 5-50 ng injected was generated. 

The experiment was then repeated with chemically synthesized 4-formamido-2,6-dinitrotoluene instead of 4-amino-2,6-dinitrotoluene. The reduction product isolated was identified as 2-amino-4-formamido-6-nitrotoluene. Using this compound as substrate, very slow formation of 2,4-diamino-6-nitrotoluene (detectable only after 96 h of incubation) could be observed. The sequence of reactions that follows 4-amino-2,6-dinitrotoluene is depicted in Figure 5. We could not obtain any evidence for a direct reduction of 4-amino-2,6-dinitrotoluene to 2,4-diamino-6-nitrotoluene. 

Figure 5. Reduction of 4-amino-2,6-dinitrotoluene (4Am-DNT) to 2,4-diamino-6-nitrotoluene (2,4DAm-NT) by non-ligninolytic cultures of R chrysosporium. The formylation of the amino group of 4Am-DNT led to 4-formamido-2,6-dinitrotoluene (4FAm-DNT). The latter is reduced to 2-amino-4-formamido-6-nitrotoluene (2Am4FAm-NT) which is subsequently deformylated.

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